The field of the present invention is that of silicone compositions which can be cured by crosslinking and which can be used in particular either as mastics or other leakproofing and/or water-repelling and/or pointing materials or alternatively to form coatings of any type (for example paints), including in particular flexible coatings of medium thickness. More specifically, the invention relates to an aqueous silicone dispersion capable of forming, by crosslinking (e.g. polycondensation) accompanied by elimination of water (preferably at room temperature), a transparent elastomer which adheres to numerous substrates. Without this being limiting, the crosslinking mechanism more especially envisaged for the conversion of the silicone, as an aqueous dispersion, to a transparent and adhesive elastomer is of the type involving hydrolysis/condensation of xe2x89xa1SiORa reactive groups with Ra=H or alkyl. The silicones or polyorganosiloxanes (POS) which come within such a context are in particular xcex1,xcfx89-dihydroxylated polydiorganosiloxanes, such as, for example, xcex1,xcfx89-di-OH polydimethylsiloxanes. In addition to this main constituent, which is a POS, aqueous silicone dispersions which are precursors of mastics or other leakproofing/water-repelling coatings optionally comprise adhesion promoters, for example silicon-comprising adhesion promoters (silanes, oligo- or polyorganosiloxanes), and optionally crosslinking agents of the trialkoxysilane type or polyfunctional resins comprising several xe2x89xa1SiORa functional groups. All these silicon-comprising constituents, when they are not hydrophilic or water-soluble, compose the non-continuous phase (silicone phase xcfx86s) of the aqueous silicone dispersion.
Aqueous silicone dispersions which are precursors of mastic, leakproofing/water-repelling or pointing materials, or of coatings form one of the latest generations of silicone compositions employed in this technical field. Their aqueous nature facilitates handling operations, shaping operations and the washing of the tools used for their application. These aqueous silicone dispersions also exhibit the advantage of a lower toxicity with respect to silicone compositions comprising organic solvents or which release volatile organic species.
The hydrophilic phase xcfx86H (non-silicone phase) of these aqueous dispersions based on silicone oil which can be crosslinked into an elastomer by (hydrolysis)/condensation with elimination of water and/or alcohol, for example, is continuous and comprises hydrophilic constituents, such as, for example, fillers (e.g. siliceous fillers) and surfactants. This hydrophilic phase xcfx86H can additionally comprise an adhesion promoter also capable of acting as crosslinking agent.
These compositions also comprise a condensation catalyst.
These aqueous dispersions of hydroxylated silicone oil can be produced conventionally by mechanical stirring or alternatively by emulsion polymerization.
The conventional method consists in employing devices of colloid mill or homogenizer type (FR-A-2 064 563, FR-A-2 114 130, FR-A-2 094 322 and EP-A-0 169 098). This technique is limited to the emulsification of polymers with a viscosity of less than 5 000 mpa.s. It is possible to mechanically emulsify more viscous oils, for example by using the techniques disclosed in FR-A-2 697 021.
It is also possible to use the technique of emulsion polymerization of cyclic or linear silicone oligomers of low molecular weight which are easy to emulsify according to conventional mechanical techniques. In this alternative, it is preferable for the surfactants also to act as polymerization catalysts (U.S. Pat. Nos. 3,294,725 and 3,360,491).
Although representing a degree of technical progress, these aqueous silicone dispersions which are precursors of mastics and/or of leakproofing/water-repelling coatings have a specification sheet, the specifications of which can be further improved. These improvable specifications are:
the stability on storage,
the excessively long curing time,
the mechanical properties of the elastomer (hardness, elasticity, resistance to abrasion),
the xe2x80x9cflowabilityxe2x80x9d of the elastomer,
the possibility of painting the elastomer,
the properties of cohesion and of adhesion of the elastomer to conventional substrates,
the problems of safety and of toxicity due to the solvents or to the alcohols formed by hydrolysis,
and the ease of use.
In the context of the invention, another specification of a more aesthetic nature but which is not without technical repercussions will also be included, namely the translucency or the transparency of the elastomer obtained after at least partial crosslinking of the aqueous silicone dispersion with elimination of water or alcohol. This transparency corresponds to a market requirement which is more particularly felt for silicone mastics.
Some proposals of the prior art have attempted to satisfy, in vain, the specification sheet which is defined above and which relates in particular to transparent aqueous silicone mastics.
European Patent Application EPA-0 542 498 relates to aqueous silicone emulsions which can be converted by crosslinking and drying into a translucent elastomer. These emulsions comprise crosslinked polydimethylsiloxane (PDMS), which is provided in the form of a dispersed phase in which less than 10% of the particles have a size of greater than 1 000 nm. This PDMS is obtained by anionic emulsion polymerization.
This emulsion also comprises a surfactant of formula RSO4M of the sodium lauryl sulphate type. The nondisperse aqueous phase of this emulsion comprises a crosslinking agent of the alkoxysilane type (xcex3-methacryloxypropyl, trimethoxysilane chloropropyltrimethoxysilane, trifluoropropyltrimethoxysilane or vinyltrimethoxysilane) and a filler composed, for example, of precipitated silica with a particle size of the order of 19 nm and of colloidal silica for which the size of the particles is approximately 20 nm. This nondisperse continuous aqueous phase also comprises a condensation catalyst of the tin octoate type.
In Example 5 of EP-A-0 542 498, the translucency obtained for the elastomer resulting from the aqueous silicone emulsions is of the order of 85% of Transmission T for a dry crosslinked elastomer film of 47 mil (1.519 mm).
The transmission T is defined according to the Lambert-Beer law:
log(100/T)=xcex5.e.C
with:
T=transmission varying from 0 less than Txe2x89xa6100% of a film with a thickness e irradiated with white light with a wavelength xcex3 of between 400 and 700 nm,
xcex5=coefficient of extinction (mmxe2x88x921),
e=thickness of the dry film (mm),
C=total fraction by volume of the non-silicone hydrophilic species in the dry film.
The translucency can be expressed by the transparency index R in %=100-T.
According to the teaching of EP-A-0 542 498, the translucency decreases when the level of silicic filler increases (page 11, line 44). It should be noted that, in accordance with the invention disclosed in EP-A-0 542 498, the achievement of an all things considered improvable translucency is dependent on the presence in the dispersed phase of at least 90% of silicone particles with a size of less than 1 000 nm. The invention disclosed in EP-A-0 542 498 is consequently based on the fineness of the silica particles.
The transparency index R of the crosslinked elastomer films obtained according to EP-A-0 542 498 is greater than 25%. In addition, the coefficient of extinction xcex5 of these films is greater than 0.8 mmxe2x88x921.
In addition, the emulsions according to EP-A-0 542 498 are restricted to those comprising a specific surfactant of the sodium lauryl sulphate type.
If the refractive index nS of the dispersed silicone phase xcfx86S and the refractive index nH of the non-silicone continuous hydrophilic phase xcfx86H of the aqueous silicone emulsions according to EP-A-0 542 498 are considered, it is apparent that |nSxe2x88x92nH| greater than 0.05. Such a |nSxe2x88x92nH| range reflects an unsatisfactory translucency for the crosslinked elastomer (xcex5 greater than 0.8 mmxe2x88x921).
Patent Application EP-A-0 739 929 discloses aqueous dispersions of polyorganodisiloxanes of the polydimethylsiloxane type which can be crosslinked into an elastomer having improved properties of stability to temperature and of transparency. According to this application, these advantages are obtained by virtue of the choice of specific surfactants, which are not alkyl sulphates, linear alkylbenzenesulphates, alkylsulphonates nor laurates. The surfactants must not behave as redistribution catalysts for siloxanes at temperatures of greater than 100xc2x0 C. Finally, the surfactants must be such that, after evaporation of the water from the silicone aqueous silicone dispersion (latex), the resulting elastomer composition comprises a crosslinked POS phase xcfx86S with a refractive index nS and a residual aqueous phase (comprising the surfactants) with a refractive index nH, nH being the same as nS.
This silicone latex is obtained by emulsifying the silicone phase/surfactant/water mixture. This results in a gelled phase with a content of silicone polymer of at least 85%. The emulsion is subsequently diluted with water. A catalyst is incorporated before or after the emulsification or before or after the dilution. It is the same as regards the crosslinking agent added.
The silicone polymer or the mixture of silicone polymers comprises an organic solvent. According to another alternative form, this aqueous silicone dispersion (silicone latex) can have a filler, for example a siliceous filler, added thereto. It is also envisaged to incorporate a stabilizing agent of the diethylamine or 2-amino-2-methyl-1-propanol type in the silicone latex.
It should be emphasized that, in accordance with the teaching of EP-A-0 739 929, page 5, line 44, transparent crosslinked elastomers can only be obtained from a silicone latex or aqueous silicone dispersion which is devoid of fillers.
The polyorganosiloxane employed is conventionally an xcex1-xcfx89-di-OH polydimethylsiloxane. The surfactant can be an alkylphenol sodium ether sulphate, an ethoxylated trisiloxane, a secondary alcohol ethoxylate, or a trimethylated ammonium chloride carrying a soybean fatty acid alkyl chain.
The catalyst is a condensation catalyst of the dibutyltin dilaurate type and the crosslinking agent is, for example, isobutyltrimethoxysilane. These silicone latices, which are precursors of elastomers and are obtained by emulsification of the silicone oil in a concentrated phase, are devoid of fillers in the examples of EP-A-0 739 929. It is under this sine qua non condition that clarity or transparency values in the vicinity of 100% can be achieved according to a test defined in EP-A-0 739 929.
In this state of the art, one of the essential objectives of the present invention is to provide an aqueous silicone dispersion:
which comprises filler(s),
which can be crosslinked into a transparent elastomer by elimination of water and/or of alcohol and/or of a carboxylic residue of the acyloxy type, preferably under ambient atmospheric conditions,
and which overcomes the deficiencies and disadvantages of the known dispersions, emulsions or latices of this type.
More particularly, the present invention is targeted at optimizing the transparency properties of the mastics and/or leakproofing/water-repelling coatings obtained by crosslinking from these aqueous silicone dispersions without sacrificing to the other specifications of the technical specification sheet, including, in particular, the stability, the elasticity, the resilience, the hardness, the mechanical strength and the adhesion to conventional substrates (glass, wood, metals or ceramics), and without giving up the low cost price.
Another essential objective of the present invention is to provide an aqueous silicone dispersion which can be correctly and sufficiently rapidly crosslinked by condensation into a transparent, filler-comprising elastomer with enduring mechanical properties.
Another essential objective of the invention is to provide an aqueous silicone dispersion of the type of that described above which is easy to use and in particular easily smoothable and washable with water (cleaning of the tools which have been used in their preparation and in their application) because of the exclusive presence of water as solvent or as liquid component of the continuous phase.
Another essential objective of the invention is to provide an aqueous silicone dispersion which is stable on storage (for example in a container, xe2x80x9cpot lifexe2x80x9d).
Another essential objective of the invention is to provide an aqueous silicone dispersion of the type of that described above which results in a transparent and filler-comprising crosslinked elastomer exhibiting an improved flame resistance.
Another objective of the invention is to provide an aqueous silicone dispersion of the type of that described above which is easy to handle and to model, in particular for the purpose of applications such as mastics and/or leakproofing/water-repelling/pointing coatings.
Another essential objective of the invention is to provide a mastic, a leakproofing/water-repelling material or a leakproofing/water-repelling coating which is translucent and which comprises abovesaid dispersion and/or the crosslinked elastomer which results therefrom.
These objectives and others are achieved by the present invention, which results from the demonstration, after lengthy studies and experiments and in an entirely surprising and unexpected way, that the adjustment of the difference in absolute value of the refractive indices of the silicone phase and of the non-silicone hydrophilic phase of a filler-comprising aqueous silicone dispersion within a range of less than or equal to 0.05 makes it possible to render sufficiently transparent the crosslinked elastomer obtained by crosslinking the aqueous silicone dispersion under consideration, even though the latter comprises a particulate filler liable to counteract the translucency.
It follows that the present invention relates to an aqueous silicone dispersion which can be crosslinked into a transparent elastomer of the type of those comprising:
(i) a silicone phase xcfx86S with a refractive index nS comprising:
at least one crosslinkable polyorganosiloxane (POS) A,
optionally at least one silicon-comprising adhesion promoter B,
optionally at least one crosslinking agent D, with the condition according to which at least one of the constituents A, B or D of xcfx86S carries at least three crosslinking functional groups per molecule,
and optionally at least one solvent Sa of the POS A silicone(s),
(ii) a non-silicone hydrophilic phase xcfx86H with a refractive index nH comprising at least one filler FI, a surfactant SA and optionally at least one catalyst and/or at least one water-soluble adhesion promoter Bxe2x80x2,
(iii) and water,
characterized in that:
|nSxe2x88x92nH|xe2x89xa60.05,
xe2x80x83preferably,
|nSxe2x88x92nH|xe2x89xa60.04.
Within the meaning of the invention, the hydrophilic phase xcfx86H comprises all the hydrophilic constituents, with the exception of the water (iii), of the dispersion.
This dispersion exhibits the advantage of being convertible by crosslinking (hydrolysis/condensation), with elimination of water and optionally of alcohol or of acyloxy units, to a cured and transparent elastomer while possessing a particulate filler, for example a siliceous filler, which makes possible a degree of adjustment of the mechanical properties of the elastomer. This possibility is particularly advantageous in applications such as mastics or leakproofing/water-repelling coatings.
Such a result could be obtained by adjustment of the refractive indices nS and nH of the silicone phase xcfx86S and of the hydrophilic phase xcfx86H respectively.
Within the meaning of the invention, the term xe2x80x9ctransparentxe2x80x9d means that the cured silicone elastomer exhibits a transparency Rxe2x89xa630%, preferably Rxe2x89xa625% and more preferably still 0%xe2x89xa6Rxe2x89xa616%. R is as defined above with respect to the transmission T given in the Lambert-Beer law for a film with a thickness e=2 mm and for exposure to radiation with a wavelength 400 nmxe2x89xa6xcexxe2x89xa6700 nm (visible).
As emerges from the condition given above in the definition of the invention, it is important for the crosslinking function to be provided by at least one of the constituents A, B, Bxe2x80x2 or D of xcfx86S. This crosslinking function assumes that at least three crosslinking functional groups (for example OH, alkoxy, acetoxy, ketiminoxy or enoxy) are present per molecule. There is no reason why the crosslinking functional groups should not be different from one another but, in practice, they are preferably only condensable silanol functional groups.
The result of this is that, according to a preferred form of the invention, the abovetargeted aqueous silicone dispersion can be converted into a transparent elastomer, this conversion being accompanied by elimination of water, advantageously by evaporation.
This water is essentially that of the aqueous phase of the emulsion and to a minor extent originates from the condensation of the hydroxyls of the silanols.
Thus, according to a preferred form of the dispersion according to the invention:
the POS A is a polyorganosiloxane oil exhibiting, per molecule, at least two condensable or hydrolysable xe2x89xa1SiORa groups with Ra=H or alkyl, Ra=H being especially preferred;
the POS A can be crosslinked by condensation or hydrolysis/condensation, optionally in the presence of a condensation catalyst C;
and the optional crosslinking agent D comprises at least one hydroxylated and/or alkoxylated silicone resin and optionally at least one alkoxysilane E which supplies the xe2x89xa1SiORa ends of the POS A.
The main constituent of the dispersion, on a weight basis, is the polyorganosiloxane POS A. The POS A preferably comprises at least one viscous and reactive silicone homopolymer or copolymer capable of forming, by polycondensation, a crosslinked three-dimensional network:
either alone, if it is tri- or polyfunctional,
or in combination with a crosslinking agent B and/or Bxe2x80x2, D and/or E, if the POS A is only difunctional.
The functionalities under consideration are crosslinking functionalities, preferably crosslinking by (hydrolysis)/condensation. These functionalities are, for example, hydroxyl or alkoxyls.
The general formula of the POS A is preferably as follows:
(RfO|aSiRc(3xe2x88x92a)xe2x80x94Oxe2x80x94"Parenopenst"SiR3R4xe2x80x94O"Parenclosest"mxe2x80x94"Parenopenst"SiR5R6xe2x80x94O"Parenclosest"nxe2x80x94"Parenopenst"SiR3RNxe2x80x94O"Parenclosest"pxe2x80x94SiR2(3xe2x88x92a)(ORf)2xe2x80x83xe2x80x83(A)
in which:
Rf=corresponds to hydrogen or a linear or branched C1-C4 alkyl optionally substituted by a linear or branched C1-C3 alkyl (for example:
methyl, ethyl, propyl, ethoxyethyl);
R3, R4, R5 and R6 are identical or different radicals chosen from:
linear or branched C1-C30 alkyls (for example: methyl . . . dodecyl),
and/or linear or branched C2-C20 alkenyls (for example: vinyl or allyl),
and/or C6-C12 aryls optionally substituted by 1 to 3 linear or branched C1-C3 alkyls (for example: phenyl or totyl),
and/or aralkyls comprising, for the aryl part, C6-C8 carbon atoms and, for the linear or branched alkyl part, C1-C4 carbon atoms (for example:
benzyl,
phenetyl or 
the radical 
and/or aralkenyls comprising, for the aryl part, C6-C8 carbon atoms and, for the linear or branched alkenyl part, C1-C4 carbon atoms (for example styryl);
RN corresponds to radicals, which are identical or different from one another, which are defined as being amine-comprising radicals, preferably aminoalkyl radicals, or alkyl radicals comprising one or more epoxide and/or carboxylic and/or methacryloxy and/or mercapto and/or isocyanate and/or isocyanurate and/or cyano functional groups;
Re represents radicals, which are identical or different from one another, which are defined as being radicals corresponding to the same definition as that given above for R3, R4, R5 and R6 and/or radicals corresponding to the same definition as that given above for RN;
a=1, 2 or 3;
m, n and pxe2x89xa70 and m, n and p are chosen such that |nSxe2x88x92nH|xe2x89xa60.05 with m+n+p greater than 200 and preferably m+n+p greater than 700.
The POS A is advantageously a silicone oil formed by a homo- or a copolymer of formula A given above, in which
Rf corresponds to hydrogen,
a=1,
Re and R3 to R6 are radicals, which are identical or different from one another, chosen from:
linear or branched C1-C15 alkyls (preferably methyl . . . dodecyl),
and/or phenyls and/or tolyls,
and/or benzyl and/or phenetyl radicals and/or radicals of formula: 
and/or styryls.
In the context of the present invention, use may especially be made of oils A prepared by the anionic polymerization process disclosed in the abovementioned U.S. Pat. No. 2,891,920 and in particular U.S. Pat. No. 3,294,725 (cited as reference). The polymer obtained is anionically stabilized by a surface-active agent which, in accordance with the teaching of U.S. Pat. No. 3,294,725, is preferably the salt of an alkali metal of a hydrocarbonaceous aromatic sulphonic acid, the free acid also acting as polymerization catalyst. The preferred catalyst and the preferred surface-active agents are dodecylbenzenesulphonic acid or alkyl sulphuric acid and their alkali metal salts, in particular their sodium salts. Other anionic or nonionic surface-active agents can optionally be added. However, this addition is not necessary as, in accordance with the teaching of U.S. Pat. No. 3,294,725, the amount of anionic surface-active agent resulting from the neutralization of the sulphonic acid is sufficient to stabilize the polymer emulsion. This amount is generally less than 3%, preferably 1.5%, of the weight of the emulsion.
This emulsion polymerization process is particularly advantageous as it makes it possible to directly obtain an emulsion comprising the oil A. Furthermore, this process makes it possible to obtain, without difficulty, oils A in an emulsion of very high viscosity.
In accordance with the invention, it will be preferable, however, to start from oils A which are already polymerized for the preparation of the dispersion by using, for example, the techniques for emulsifying the silicone phase disclosed in FR-A-2 697 021.
Furthermore, it is preferable for the viscosity xcex7 at 25xc2x0 C. of these POS A to be at least 100 mPa.s, preferably at least 50 000 mPa.s. This is because it is in particular for viscosities xcex7 of greater than 50 000 mpa.s that an elastomer is obtained which exhibits an array of suitable mechanical properties, in particular with regard to the Shore A hardness and the elongation. In addition, the higher the viscosity, the more the mechanical properties are retained during the ageing of the crosslinked elastomer which can be obtained from the aqueous dispersion. The viscosities xcex7 at 25xc2x0 C. chosen in practice within the context of the invention are between 5xc3x97104 and 15xc3x97105 mPa.s.
All the viscosities dealt with in the present account correspond to a dynamic viscosity quantity at 25xc2x0 C. referred to as xe2x80x9cNewtonianxe2x80x9d, that is to say the dynamic viscosity which is measured, in a way known per se, at a shear rate gradient which is sufficiently low for the viscosity measured to be independent of the rate gradient.
The optional adhesion promoters B and Bxe2x80x2 of the phases xcfx86S and xcfx86H respectively can correspond to any known product, including in particular:
(i) An amine-comprising and silicon-comprising
compound, which is optionally salified, formed of several repeat units of following mean formula (I):                               R          x          10                ⁢                                            R              y              20                        ⁡                          (                              OR                30                            )                                z                ⁢                  SiO                                    4              -                              (                                  x                  +                  y                  -                  z                                )                                      2                                              (        I        )            
xe2x80x83in which:
R10 represents a nitrogen-free monovalent group, identical or different in nature from one repeat unit to another, corresponding to hydrogen, a C1-C6 alkyl, an aryl or a C2-C8 alkenyl which is optionally substituted, preferably by a halogen or halogenated radical, R10 being selected more particularly from the group consisting of H and optionally halogenated C1-C4 alkyl, the methyl, ethyl, propyl, 3,3,3-trifluoropropyl, vinyl, allyl and phenyl groups being more especially preferred;
R20 represents a hydrocarbonaceous monovalent group bonded to the silicon via an Sixe2x80x94C bond and comprising at least one nitrogen atom, R20 being identical or different in nature from one repeat unit to another;
R30 is a hydrocarbonaceous group comprising from 1 to 18 carbon atoms and preferably corresponding to the same definition as that given above for R10,
x, y and z are integers or positive decimal numbers of less than 4,
and x+y+z less than 4.
This amine-comprising and silicon-comprising compound (i) is as disclosed in French Patent Application FR-A-2 724 661, for which further reference may be made to the details therein. In the case where this promoter (i) exhibits a certain amine content (e.g. at least one amine function group per silicon) and/or is salified (according to the pH), said promoter (i) is then hydrophilic, indeed even water-soluble, and corresponds to a promoter Gxe2x80x2 included in xcfx86H.
(ii)
(ii.1) a silane substituted by hydroxyls or alkoxyls and hydrophilic functional groups for anchoring to the substrate, such as amines (e.g. aminopropyltrihydroxysilane), and/or their hydrolysis and/or condensation products.
(ii.2) linear hydroxylated polydiorganosiloxanes with D and/or MD siloxyl units; mention may be made, as example of polydiorganosiloxane, of hydroxylated polymethylsiloxane.
(ii.3) a hydroxylated POS resin comprising T and optionally M and/or D and/or Q siloxyl units or alternatively Q and M and/or D and/or T siloxyl units.
Mention may be made, as examples of resins, of T(OH), DT(OH), DQ(OH), DT(OH), MQ(OH), MDT(OH), MDQ(OH) and the mixtures of these. In addition to the OH groups, these promoters (ii.3) each comprise one or more functional groups for anchoring to a substrate, which functional groups are identical or different from one another and are chosen from the group consisting of the amino-, epoxy-, acrylo-, methacrylo-, ureido-, mercapto-, chloroalkyl- and preferably aminoalkyl (aminopropyl) functional groups.
For more details with regard to these promoters (ii), reference will be made to French Patent Application FR-A-2 753 708, which fully describes this promoter.
As soon as the product forming the promoter (ii) has a hydrophilic nature, indeed even water-soluble nature, it comes within the category of the hydrophilic promoters Bxe2x80x2 of xcfx86H. This is in particular the case when (ii) is salified and/or when it is an amine-comprising organosilicon compound comprising at least one amine function group per silicon.
(iii) A nitrogenous adhesion promoter of the potassium N-(2-aminoethyl)-3-aminopropylmethylsilanolate type or of the polydimethylsiloxane functionalized by 3-(2-aminoethylamino)propyl units type according to EP-A-0 572 006.
(iv) A siliconate Rxe2x80x94Si(OM)3 or its condensation products with M=K30, Na30  or NH4+ cation, these siliconates or derivatives (iv) being, because of their salified nature, hydrophilic promoters Bxe2x80x2 present in xcfx86H.
(v) Organotrialkoxysilanes (such as vinyltrimethoxy-silane) and alkyl silicates, such as methyl silicate or ethyl silicate or their partial hydrolysis/condensation products, that is to say alkyl polysilicates, such as methyl polysilicate and ethyl polysilicate, at a content of 0.1 to 20 parts of adhesion agent per 100 parts by weight of POS A.
The organotrialkoxysilanes and the alkyl silicates preferably correspond to the general formula:
R10pSi(OR11)4xe2x88x92p
xe2x80x83in which:
R11 is an alkyl radical having from 1 to 4 carbon atoms,
R10 corresponds to the same definition as R11 or to a vinyl.
(vi) Organodi(or tri)alkoxysilanes comprising epoxy, carboxylic, methacryloxy, mercapto, isocyanate, isocyanurate or cyano groups and the hydrolysis and condensation products of these organoalkoxysilanes.
(vii) Titanates or zirconates (chelated or non-chelated).
It should be added, as regards the promoters B and Bxe2x80x2 defined above of (i) to (vii), that a person skilled in the art is entirely able to identify and to choose from the products thus defined, on the one hand, those which are hydrophilic and which are capable of forming the promoters Bxe2x80x2 of xcfx86H and, on the other hand, those which do not have this hydrophilic nature and which can be employed as promoter B in xcfx86S.
As regards the optional crosslinking agent D, which alone or in addition to the POS A and/or to the promoter B and/or Bxe2x80x2 takes on the role of crosslinking agent, one of its essential characteristics is to be soluble in xcfx86S or dispersible in the silicone phase xcfx86S in the form of nanometric particles.
It can be itself also formed of at least one hydroxylated and/or alkoxylated silicone resin having a content by weight of hydroxyl and/or alkoxyl groups of between 0.1 and 10%, preferably between 0.4 and 4%.
This resin D exhibits, per molecule, at least two different units chosen from those of formula M, D, T and Q, at least one being a T or Q unit.
Mention may be made, as examples of organic substituents of these units, of the methyl, ethyl, isopropyl, tert-butyl, n-hexyl and phenyl radicals.
These silicone resins are well-known branched organo-polysiloxane polymers, the processes for the preparation of which are disclosed in a great many patents.
Mention may be made, as examples of resins which can be used, of MQ resins, MDQ resins, TD resins and MDT resins.
Use may be made of resins which are solid or liquid at room temperature. These resins can be incorporated as such in the emulsions in the POS A, in solution in an organic solvent or a silicone oil, or else in the form of aqueous emulsions (EP-A-0 359 676).
Aqueous emulsions of silicone resins which can be used are, for example, disclosed in U.S. Pat. Nos. 4,028,339, 4,052,331, 4,056,492, 4,525,502 and 4,717,599 cited as reference.
As indicated above, this optional resin D can act as crosslinking agent by virtue of its hydroxyl and/or alkoxyl functional groups, which are capable of reacting by condensation with the ORa groups of the silicone oil A.
According to another alternative form, the optional crosslinking agent D can be formed by the above described (optionally salified) aminoalkylated silicone resin (i), the latter comprising, for this purpose, molecules having at least three OR3 groups per molecule, which corresponds to w+yxe2x89xa62 in (I).
It should be noted that, in the alternative forms of the type of those described above where the cross-linking agent D can be formed by the hydrophilic promoter Bxe2x80x2 present in xcfx86H, this crosslinking agent D/Bxe2x80x2 consequently has the property of being soluble in xcfx86H or dispersible in xcfx86H in the form of nanometric particles.
The alkoxysilane E can play the same crosslinking role as D. However, it can only react with the silicone oil A provided that a prior hydrolysis of the ORa functional groups is carried out.
Mention may be made, as examples of alkoxysilane E, of ViSi(OEt)3, ViSi(OMe)3, Si(OEt)4, MeSi(OMe)3 or Si(OMe)4, Me=CH3 and Et=CH3CH2. According to alternative forms, the crosslinking agent E can also be chosen from the following products: siliconate, silicate, silica (powdered or colloidal and their mixtures). If appropriate, these products can be used in combination with the abovementioned silicone resins.
As regards the catalyst C, it is preferably a catalytic tin compound. The latter is generally an organotin salt preferably introduced in the form of an aqueous emulsion. The organotin salts which can be used are described in particular in the work by Noll, Chemistry and Technology of Silicones, Academic Press (1968), page 337.
Use may also be made, as catalytic tin compound, of the reaction product of a tin salt, in particular of a tin dicarboxylate, with ethyl polysilicate, as disclosed in Patent U.S. Pat. No. 3,862,919.
The reaction product of an alkyl silicate or of an alkyltrialkoxysilane with dibutyltin diacetate, as disclosed in Belgian Patent BE-A-842 305, may also be suitable.
According to another possibility, recourse is had to a tin(II) salt, such as SnCl2 or stannous octoate. The preferred tin salts are tin bischelates (EP-A-147 323 and EP-A-235 049) or diorganotin dicarboxylates, in particular dibutyl- or dioctyltin diversatates (British Patent GB-A-1 289 900), dibutyl- or dioctyltin diacetate, or dibutyl- or dioctyltin dilaurate. Use is made of 0.01 to 3, preferably of 0.05 to 2, parts of organotin salt per 100 parts of A. According to alternative forms, use may also be made, as catalyst F, of strong acids or bases (KOH, NaOH) or amines (optionally the amine of the resin C).
Several embodiments of the dispersion can be envisaged in satisfying the essential characteristics of the dispersion according to the invention, namely |nSxe2x88x92nH|xe2x89xa60.05.
According to a first embodiment, the dispersion comprises at least one POS A1 with a refractive index nA1 such that |nA1xe2x88x92nH| greater than 0.04, this POS A1 furthermore being used in combination with at least one agent for enhancing the nS preferably chosen from the solvents Sa of the POS A1, this enhancing agent furthermore being present in proportions chosen such that it is miscible with xcfx86S.
The POS A1 is preferably a silicone oil formed by an xcex1,xcfx89-diOh diorganopolysiloxane of following formula: 
in which:
R1, R2 are radicals which are identical or different from one another and correspond:
to a linear or branched C1-C6 alkyl, preferably to a methyl, an ethyl, a propyl, a butyl, a pentyl or a hexyl,
or to a linear, branched or cyclic C1-C6 alkenyl, preferably a vinyl;
RN and R3 are as defined above in the formula (A);
qxe2x89xa710;
p1xe2x89xa70.
These organic radicals R1, R2, R3 and R4 can additionally be optionally substituted by cyano or fluoro groups. As regards the radicals R1, R2 and R3, the substituents generally used, because of their availability in industrial products, are the methyl, ethyl, propyl, vinyl and 3,3,3-trifluoropropyl radicals. Generally, at least 80% by number of these radicals are methyl radicals.
In practice, xcex1-xcfx89-dihydroxypolydimethyl-siloxanes with 
ends will be favoured as POS A1.
The agent for enhancing the nS has a refractive index nR which can be defined as follows:
nR greater than nA1,
and preferably nR greater than nH.
In practice, nR is, e.g., such that nR greater than 1.460, preferably nRxe2x89xa71.475.
This agent for enhancing the nS is advantageously selected from the group of compounds consisting of:
a) at least one liquid paraffin (monomer and/or oligomer and/or polymer);
b) at least one alkyl phthalate comprising a linear or branched alkyl residue having from 1 to 13 carbon atoms (monomer);
c) at least one alkylaromatic with a molecular weight xe2x89xa7200 g/mol (monomer and/or oligomer and/or polymer),
d) and their mixtures.
The enhancing agent is preferably chosen from the alkylaromatic compounds c) and more preferably still from the following compounds C:
xcex1) a monoalkylbenzene comprising a linear or branched alkyl residue having from 9 to 30 carbon atoms,
xcex2) a dialkylbenzene comprising linear or branched alkyl residues having from 5 to 25 carbon atoms,
xcex3) a diphenylalkane comprising a linear or branched alkane residue having from 4 to 25 carbon atoms,
xcex4) an alkylate comprising at least one monoalkylbenzene xcex1 and/or at least one dialkylbenzene xcex2 and/or at least one diphenylalkane xcex3.
For more details regarding these alkylaromatic compounds c), reference will be made to Patent FR-A-2 446 849.
Mention may be made, as examples of commercial compounds c), of those sold by Chevron under the trade name xe2x80x9calkylat Progiline 155xe2x80x9d.
The mean composition of this alkylat Progiline is a mixture based on:
35-50% by weight of monoalkylbenzenes comprising branched alkyl residues having from 12 to 25 carbon atoms,
and 65-50% by weight of meta- and para-dialkylbenzenes comprising branched alkyl residues having from 16 to 20 carbon atoms.
It is obvious that this enhancing agent for the nS is used in proportions chosen such that it is miscible with xcfx86s.
In the context of a second embodiment of the dispersion according to the invention, provision is made for the use of a POS A2 having a refractive index nA2 relatively close to that nH of the silicone phase xcfx86H. Thus, according to this second embodiment, the dispersion comprises at least one POS A2 with a refractive index nA2 chosen such that |nA2xe2x88x92nH|xe2x89xa60.04, the POS A2 thus preferably belonging to the family of the diorganosiloxane copolymers of following formula (A2): 
in which:
R3 and R4 are radicals, which are identical or different from one another, each comprising a linear or branched C1-C6 alkyl, preferably a methyl, an ethyl, a propyl, a butyl, a pentyl or a hexyl;
R5 are radicals, which are identical or different from one another, each comprising:
a linear or branched C1-C6 alkyl, preferably a methyl, an ethyl, a propyl, a butyl, a pentyl or a hexyl;
and/or a phenyl and/or a tolyl;
and/or a benzyl and/or a phenetyl and/or a radical of formula: 
and/or a styryl;
R6 are radicals, which are identical or different from one another, each comprising:
a linear or branched C7-C15 alkyl, preferably an octyl, a nonyl and/or a dodecyl;
and/or a phenyl and/or a tolyl;
and/or a benzyl and/or a phenetyl and/or a radical of formula: 
and/or a styryl;
Re corresponding to any one of the definitions given above for R3, R4, R5 and R6;
RN and R3 being as defined above in the key to the formula (A);
a=1;
m, n and pxe2x89xa70; m and n are such that |nSxe2x88x92nH| less than 0.05, with m+n greater than 200, preferably m+n greater than 700.
It is important to emphasize that these copolymers A2 can be block or random copolymers. Mention may be made, as examples of POS A2, of:
poly(diphenyl)(dimethyl)siloxane,
poly(methylphenyl)(dimethyl)siloxane,
poly(methyloctyl)(dimethyl)siloxane,
poly(methyldodecyl)(dimethyl)siloxane,
poly(methylaryl)(dimethyl)siloxane, in which the aryl substituents are, for example, phenetyls and/or styryls and/or aryls of formula: 
According to an alternative form of the second embodiment, the POS A2 defined by |nA2xe2x88x92nH|xe2x89xa60.04 is used in combination with at least one agent for enhancing the ns preferably chosen from the solvents Sa of the POS A2, this enhancing agent furthermore being present in proportions chosen such that it is miscible with xcfx86S.
This agent for enhancing the ns has a refractive index nR and has been defined above in the context of the description of the first embodiment of the invention.
In accordance with a third embodiment of the dispersion according to the invention, this third embodiment being a result of the first two embodiments, said dispersion comprises at least one POS A1 with a refractive index such that |nA1xe2x88x92nH| greater than 0.04 and at least one POS A2 with a refractive index such that |nA2xe2x88x92nH|xe2x89xa60.04, A1 and A2 furthermore being at least partially miscible with one another.
According to an alternative form of this third embodiment, the dispersion additionally comprises at least one agent for enhancing the refractive index nS of the silicone phase preferably chosen from the solvents S common to POS A1 and to POS A2, this enhancing agent furthermore being present in proportions chosen such that it is miscible with xcfx86S. In this alternative form, the enhancing agent is a solvent S of A1 and A2 (third-party solvent). It follows from this that the miscibility of A1 and A2 when they are alone is no longer a necessary condition. This third-party solvent S can be selected from the solvents Sa as defined above.
In accordance with the invention, an alternative to the step presented above of adjusting |nSxe2x88x92nH| by varying the rise in the refractive index nS of the silicone phase xcfx86S would be to lower the refractive index nH of the non-silicone hydrophilic phase xcfx86H.
It follows from this that a fourth embodiment of the dispersion is provided in accordance with the invention, according to which embodiment the dispersion is characterized in that xcfx86H comprises at least one surfactant SA selected from ionic, nonionic or amphoteric fluorinated surfactants and their mixtures, preferably from the group of compounds consisting of:
perfluoroalkyls,
perfluorobetaines,
ethoxylated polyfluoroalcohols,
polyfluoroalkylammoniums,
surface-active agents, the hydrophilic part of which comprises one or more saccharide unit(s) carrying from five to six carbon atoms and the hydrophobic part of which comprises a unit of formula Rf(CH2)nxe2x80x94, in which n=2) 20 and Rf represents a perfluoroalkyl unit of formula CmF2m+1, in which m=1 to 10;
polyelectrolytes exhibiting fatty perfluoroalkyl side groups;
SA furthermore having a refractive index nSAxe2x89xa61.5, preferablyxe2x89xa61.43.
The term xe2x80x9cfluorinated surface-active agentxe2x80x9d is understood to mean, as is fully known per se, a compound formed of an aliphatic perfluorocarbonaceous part comprising at least three carbon atoms and an ionic, nonionic or amphoteric hydrophilic part. The perfluorocarbonaceous part of at least three carbon atoms can represent either the whole or only a fraction of the fluorocarbonaceous part of the molecule. A large number of references regarding this type of compound are found in the literature. A person skilled in the art may refer in particular to FR-A-2 149 519, WO-A-94 21 233, U.S. Pat. No. 3,194,767 or the work xe2x80x9cFluorinated Surfactantsxe2x80x9d, Erik Kissa, published by Marcel Dekker Inc., chapter 4, in particular Tables 4.1 and 4.4. Mention may in particular be made of the products sold by Du Pont Chemicals under the name Zonyl(copyright), for example FSO, FSN, FS-300 or FSD, the fluorinated surfactants with the name Forafac(copyright) distributed by Elf Atochem and the products sold under the name Fluorad(copyright) by 3M. Mention will in particular be made, among the surfactants, of anionic, cationic, nonionic and amphoteric perfluoroalkylated compounds and, among these, more particularly of surfactants of the class of the Zonyl(copyright) products sold by Du Pont, e.g.:
F(CF2CF2)3-8CH2CH2SCH2CH2COOLi (anionic),
F(CF2CF2)3-8CH2CH2O(CH2CH2O)yH (nonionic)
F(CF2CF2)3-8CH2CH2SCH2CH2N+(CH3)3CH3SO4xe2x88x92 (amphoteric)
F(CF2CF2)3-8CH2CH(OCOCH3)CH2N+(CH3)2CH2CH2CO2xe2x88x92 (amphoteric),
sold by Du Pont under the names Zonyl(copyright) FSA, Zonyl(copyright) FSO, Zonyl(copyright) FSC and Zonyl(copyright) FSK respectively.
There may more specifically be named, in connection with these products:
Zonyl(copyright) FSO 100: CAS 65545-80-4, (nonionic), 99 to 100%, the remainder being 1,4-dioxane
Zonyl(copyright) FSN: CAS 65545-80-4, 99 to 100%, the remainder being sodium acetate and 1,4-dioxane
Zonyl(copyright) FS-300: CAS 65545-80-4, 40%, the remainder being 1,4-dioxane ( less than 0.1%) and water
Zonyl(copyright) FSD: CAS 70983-60-7, 30%, (cationic), the remainder being hexylene glycol (10%), sodium chloride (3%) and water (57%).
Mention may also be made of:
perfluoroalkylbetaines (amphoteric) such as that sold by Elf Atochem under the name Forafac 1157, ethoxylated polyfluoroalcohols (nonionic), such as that sold by Elf Atochem under the name Forafac 1110 D, and polyfluoroalkylammonium salts (cationic), such as that sold by Elf Atochem under the name Forafac 1179;
surface-active agents, the hydrophilic part of which comprises one or more saccharide unit(s) comprising from 5 to 6 carbon atoms (units derived from sugars such as fructose, glucose, mannose, galactose, talose, gulose, allose, altose, idose, arabinose, xylose, lyxose and/or ribose) and the hydrophobic part of which comprises a unit of formula RF(CH2)n where n can range from 2 to 20, preferably from 2 to 10, and RF represents a perfluoroalkyl unit of formula CmF2m+1 with m being able to range from 1 to 10, preferably from 4 to 8, chosen from those exhibiting the characteristics defined above. Mention may be made of the monoesters of perfluoroalkylated fatty acids and of sugars such as xcex1,xcex1-trehalose and sucrose, it being possible for the monoester functional group to be represented by the formula RF(CH2)nC(O) where n can range from 2 to 10 and RF represents a perfluoroalkyl unit of formula CmF2m+1 with m being able to range from 4 to 8, which are described in JAOCS, Vol. 69, No. 1 (January 1992) and are chosen from those exhibiting the characteristics defined above;
polyelectrolytes exhibiting fatty perfluoroalkyl side groups, such as polyacrylates exhibiting RF(CH2)n groups where n can range from 2 to 20, preferably from 2 to 10, and RF represents a perfluoroalkyl unit of formula CmF2m+1 with m being able to range from 1 to 10, preferably from 4 to 8, chosen from those exhibiting the characteristics defined above; mention may be made of the polyacrylates exhibiting xe2x80x94CH2C7F15 groups described in J. Chim. Phys., (1996) 93, 887-898, and chosen from those exhibiting the characteristics defined above.
According to a preferred characteristic of this fourth embodiment, the dispersion is characterized by a concentration of SA, expressed as % by weight with respect to xcfx86H, is the following:
0.5xe2x89xa6[SA]xe2x89xa610,
preferably, 1xe2x89xa6[SA]xe2x89xa66.
Naturally, SA can be composed of one or more fluorinated surfactants in combination with other surfactants, without this being harmful to the transparency of the final elastomer.
In the same way that surfactants are selected having a reduced refractive index nSA similar to that of the silicone phase, in order to lower the index nH of xcfx86H, it can be envisaged, according to other embodiments, to select the constituents of xcfx86H from those having a low refractive index and thus liable to lower the overall index nH.
Furthermore, the present invention also encompasses the case according to which there would exist a dispersion where at least one of the constituents of the silicone phase xcfx86S would be chosen for its refractive index sufficiently close to nH and at least one of the constituents of the non-silicone hydrophilic phase xcfx86H would be chosen for its index sufficiently low to be close to, indeed even less than or equal to, nS.
The aqueous silicone dispersion according to the preferred embodiments defined above makes it possible to obtain a final elastomer which satisfies the specification sheet and which in particular has transparency characteristics such that the coefficient of extinction xcex5, expressed in mmxe2x88x921, is xe2x89xa61, preferably xe2x89xa60.8, respectively for |nHxe2x88x92nS|xe2x89xa60.05 and for |nHxe2x88x92nS|xe2x89xa60.04.
This transparency is obtained notwithstanding the presence of a filler, preferably a silicic filler, essential for improving the mechanical properties of the final elastomer.
According to even more preferred embodiments, the dispersion is characterized by the following composition, in parts by weight on a dry basis:
100 of at least one POS A1 of the xcex1,xcfx89
dihydroxylated polydimethylsiloxane silicone oil kind, or of at least one POS A2 of the xcex1,xcfx89
dihydroxylated copolymer silicone oil kind:
with dimethylsiloxane units and with diphenylsiloxane units,
with methyl(alkylstyryl)siloxane units and with dimethylsiloxane units,
with methyl(octyl or dodecyl)siloxane units and with dimethylsiloxane units, or
with methylphenylsiloxane units and with dimethylsiloxane units;
0 to 10 of at least one adhesion promoter B and/or Bxe2x80x2 chosen from amine-comprising silicone resins or oligomers comprising D, T and/or Q, optionally M, siloxyl units, at least part of the D, T or M units carrying one or more amine functionalities D(N) and/or T(N) and/or and/or from hydroxylated linear POSs and/or hydroxylated silicone resins, preferably from resins of the T(OH), DT(OH), DQ(OH), DT(OH), MQ(OH), MDT(OH) or MDQ(OH) kind and their mixtures;
0 to 10 of at least one crosslinking agent D chosen:
from hydroxylated silicone resins, preferably from resins of the T(OH), DT(OH), DQ(OH), DT(OH), MQ(OH), MDT(OH) or MDQ(OH) kind and their mixtures, these resins having silicons substituted by vinyl and/or phenyl and/or 3,3,3-trifluoropropyl and/or linear or branched C1-C6 (advantageously C1) alkyl radicals,
and/or silicas;
0 to 5 of at least one alkoxysilane E of formula Rb3xe2x88x92tSi(ORa)t with Ra as defined above, Rb=optionally substituted C1-C6 (cyclo)alkyl or alkenyl and t=1, 2 or 3;
0 to 30 at least one solvent Sa of the POS A, preferably comprising an alkyl-benzene(co)polymer;
0 to 2 of at least one condensation catalyst C;
0.5 to 10 of at least one surfactant SA;
2 to 20 of at least one siliceous filler FI preferably selected from the following products: precipitated or non-precipitated silica, colloidal or powdered silica and mixtures of these products;
0 to 20 of at least one silicon-comprising additive SC, such as sodium silicate or such as organosilicate;
with the condition according to which at least one of the components D, B, Bxe2x80x2 or E is present in the composition.
The fillers FI employed can for example be reinforcing siliceous fillers FI.
Such siliceous fillers have a particle size generally of between a few nanometres of 300 xcexcm and a BET [lacuna] surface of greater than 50 m2/g.
These siliceous fillers are chosen, e.g., from colloidal silicas, combustion and precipitation silica powders or their mixtures.
These silicas are well known; they are used in particular as fillers in silicone elastomer compositions which can be vulcanized under hot conditions to a silicone rubber. These silicas exhibit a mean particle size generally of less than 0.1 xcexcm and a BET specific surface preferably of between 100 and 350 m2/g.
Use may also optionally be made (at a low dose) of semi-reinforcing siliceous fillers, such as diatomaceous earths, crushed quartz or optionally an alumina hydrate or a titanium dioxide, with the proviso that such fillers are sufficiently fine not to be harmful to the transparency (nanometric fillers).
Use will preferably be made of colloidal silicas which are provided in the form of fine silica particles (less than or equal to 100 nm) predispersed in water or organic polymer (non-silicone) nanolatices, such as claimed in Application PCT WO-A-97/47 687. These fillers FI are introduced into the emulsion in the form of a dry powder or in the form of colloidal dispersions, for example by simple mixing.
In addition to the fluorinated surfactants defined above, it is also possible to employ non fluorinated surfactants SA which are selected, for example, from the salts of the alkali metals of hydrocarbonaceous aromatic sulphonic acids or alkyl sulphuric acids and the preferred nonionic surface-active agents are polyoxyethylenated alkylphenols or polyoxyethylenated fatty alcohols.
The amount of surfactant which can be used is that commonly employed for the emulsification as disclosed in particular in the abovementioned patents and in U.S. Pat. No. 2,891,920.
The nonionic (preferably), ionic or amphoteric surfactants can be employed alone or as a mixture with one another.
Various additives can be added to the dispersions according to the invention. These additives make it possible to modify their properties and those of the final elastomers.
Thus, the dispersion moreover optionally comprises at least one dispersing agent F and/or at least one plasticizer G and/or at least one fungicidal agent H and/or at least one antifoaming agent I and/or at least one stabilizing or thickening agent J and/or at least one base K and/or one pigment or dye L (inorganic or organic).
The dispersing agents F can be composed, for example, of sodium polyacrylates and or of sodium hexameta-phosphate.
The plasticizers G are preferably chosen from unreactive (blocked) silicone oils and/or from products which enhance the index nS of xcfx86S (solvents Sa and S), such as those described above and in particular alkylbenzenes and especially those disclosed in Patent Application FR 2 446 849.
The stabilizing or thickening agents J can be carboxy-methylcellulose or xanthan gum.
Mention may be made, as examples of pigments or dyes L, of:
carbon black, aluminium oxide, expanded or non expanded vermiculite, calcium carbonate, zinc oxide, mica, talc, iron oxide, barium sulphate, slaked lime and their mixtures.
According to a preferred form of the invention, the aqueous silicone dispersion which can be crosslinked into an adhesive elastomer is a filler-comprising oil-in-water emulsion, the solids content of which is greater than or equal to 40% by weight, preferably to 80% by weight, and more preferably still between 80% and 95% by weight.
According to an advantageous alternative form, the dispersion of the invention as defined above is additionally characterized in that it comprises droplets of dispersed silicone phase xcfx86S provided in an at least partially crosslinked form.
The dispersion can be stocked in this form, before use, in an appropriate packaging with air excluded (such as, e.g., a container for application of mastic). And it is only after application to a substrate that the droplets of xcfx86S combine by coalescence to form a homogeneous material which subsequently completes its conversion to elastomer by crosslinking and elimination of water (evaporation).
The dispersions according to the invention are more particularly suitable in the building industry, in the production of mastics, of draughtproofing and leakproofing materials, such as seals, or alternatively for preparing films, coatings or other thin layers.
According to another of its aspects, the present invention relates to a process for the preparation of the dispersion as defined above. This process is characterized in that it consists essentially in producing an emulsion of at least a portion of the silicone phase xcfx86S in an aqueous phase comprising at least a portion of the hydrophilic phase xcfx86H and/or water using mechanical stirring means.
Thus, in accordance with the invention, the silicone phase xcfx86S which is emulsified in the aqueous phase comprises all or part of its constituents [(A), (B), (Sa), (S), (D) or (E), inter alia] before the stage of emulsification proper (mixing/homogenization-stirring) with the aqueous phase takes place.
According to an embodiment of the process of the invention, a silicone phase xcfx86S comprising only at least a portion of the POS A is emulsified with the aqueous phase comprising all or part of the non-silicone hydrophilic phase xcfx86H [(SA), (Bxe2x80x2), (C) or (FI), inter alia] and a small amount of water. This emulsification in a concentrated phase (5 to 10% by weight of water with respect to the total mass of POS A oil employed) is followed by the incorporation or by the successive incorporations, or not, of the other components of the phases xcfx86S and xcfx86H and water.
According to another embodiment, on the one hand, the silicone phase xcfx86S is prepared by mixing all these constituents and, on the other hand, the hydrophilic phase xcfx86H is prepared by mixing all these constituents, and then xcfx86S is subsequently emulsified in xcfx86H while also incorporating the water.
All the other alternative forms for the preparation of the dispersion can be envisaged. It is thus possible first of all to mix the POS A and a portion of the crosslinking agent D and subsequently to emulsify with the aqueous phase comprising all or part of xcfx86H and all or part of the water. The incorporation of the remainder of the constituents of xcfx86S and optionally of xcfx86H and of the water in the emulsion subsequently taking place according to one or more additions.
In any case, it is preferable for the filler FI of xcfx86H to be added to the mixture after the emulsification.
The emulsification is advantageously carried out using conventional homogenizing and stirring means, such as, for example, kneaders, planetary mixers, colloid mills, extruders of the single- or twin-screw type or homogenizers, at a temperature for example of between 10 and 50xc2x0 C. The pH is optionally adjusted between 4 and 13 by addition of organic or inorganic acid or base (e.g. potassium hydroxide or amine).
The final dispersion obtained is homogenized and then degassed and it is subsequently packaged in a packaging with air and water vapour excluded.
For the mastic and/or leakproofing/water-repelling material application, the solids content of the dispersion is preferably between 80 and 95% by weight.
As regards the coating, film or paint which can be crosslinked into a thin layer application, this solids content is advantageously between 40 and 75% by weight.
The preparations described above corresponding to the production of a precursor system of the crosslinked form of the dispersion of the invention, said precursor being provided in a single-component form which can be crosslinked by elimination of water, for example by virtue of the drying which results from being placed under ambient conditions.
The preferred precursor system according to the invention is of the single-component type.
However, it can also be a multi-component system, for example a twin-component system, which can be crosslinked by mixing the components immediately before application.
A twin-component system is formed by two separate parts P1 and P2 intended to be mixed to form the dispersion, one of these parts P1 or P2 comprising the oil A and the other the crosslinking agent, the catalyst F optionally being present in only one of the parts P1 or P2.
Another subject-matter of the invention is all the final products, including in particular mastics, transparent and adhesive leakproofing/water-repelling materials or coatings, or films, paints or coatings of medium thickness comprising the dispersion and/or the crosslinked elastomer obtained by drying this dispersion.
The invention is also targeted at the at least partially crosslinked silicone elastomer as defined above in that it is obtained from the dispersion according to the invention, preferably according to a crosslinking by condensation.
By virtue of their transparency, the dispersions and the crosslinked elastomers according to the invention are liable to have numerous outlets in the field of mastics, of leakproofing materials, of materials for forming coatings as thin layers, of films or of paints, inter alia. This transparency is all the more advantageous as it is obtained without prejudice to the other specifications of the products under consideration. The examples which follow will make possible a better understanding of the invention and will make it possible to grasp all its advantages and its alternative embodiments thereof.